Grantee Research Project Results
2003 Progress Report: New Chemical Analysis Tools for Aromatic Hydrocarbons
EPA Grant Number: R829415E02Title: New Chemical Analysis Tools for Aromatic Hydrocarbons
Investigators: Campiglia, Andres D. , Swenson, Orven F. , Borgerding, Anthony J.
Institution: North Dakota State University Main Campus , University of North Dakota
EPA Project Officer: Chung, Serena
Project Period: September 1, 2001 through August 31, 2003 (Extended to February 28, 2005)
Project Period Covered by this Report: September 1, 2002 through August 31, 2003
Project Amount: $499,105
RFA: EPSCoR (Experimental Program to Stimulate Competitive Research) (2000) RFA Text | Recipients Lists
Research Category: EPSCoR (The Experimental Program to Stimulate Competitive Research)
Objective:
This Science and Engineering Environmental Research (SEER) project is a focused, multidisciplinary, multi-institutional approach to developing new analysis methodology for an important class of organic contaminants: the aromatic hydrocarbons. The specific objective of this research project in the SEER section is to develop improved methodology for the selective chemical analysis of polycyclic aromatic hydrocarbons (PAHs); the BTEX compounds—benzene, toluene, ethylbenzene, and xylene; and the halogenated benzene compounds.
Progress Summary:
In the past year, Dr. Anthony Borgerding funded four undergraduate students who performed various projects related to the aromatic selective laser ionization detector (ArSLID). These projects included studies to determine the degree of improvement in selectivity and sensitivity offered for aromatic compounds with various substituent groups. Analysis of mixtures containing these compounds using a fast gas chromatograph (GC) system and ArSLID was compared to analyses using the same chromatographic system, with competitive detectors such as photo ionization detectors and flame ionization detectors (FID). The results of these studies were included in a manuscript that is in its final stages of acceptance at the journal Analytical Chemistry.
In addition, Dr. Borgerding’s research group redesigned and built a second version of the detector to improve performance. Specifically, the new detector has a higher maximum temperature because any connections made with low temperature adhesives were eliminated and replaced with screws and ceramics. Furthermore, the new detector is more efficient because the ionization cell volume has been minimized by a factor of 100, resulting in a lower purge gas requirement and a shorter flight path for ions. All of this should result in a detector that is not only more sensitive, but also is more robust.
Dr. Andres Campiglia reports that a method for the analysis of dibenzo[a,1]pyrene in high performance liquid chromatography (HPLC) fractions and water samples has been developed. The experimental results will be submitted for publication shortly to Environmental Science & Technology and/or Applied Spectroscopy. Their studies will provide the analyst with the following information:
• The research will provide the spectral characteristics of dibenzo[a,1]pyrene and its isomers at 77 K and 4.2 K in n-octane. It will show that dibenzo[a,1]pyrene can be determined in the presence of the other dibenzopyrene isomers at concentration ratios lower than 1:100.
• The research will provide chromatographic retention times for the five dibenzopyrene isomers under the U.S. Environmental Protection Agency (EPA) 550.1 method of analysis. Based on this parameter, they identified the potential interferents among the 16 U.S. EPA PAHs. They demonstrate that the coeluted U.S. EPA PAHs do not interfere in the analysis of dibenzo[a,1]pyrene by laser-excited time-resolved Shpol’skii spectroscopy (LETRSS).
• The research will provide analytical figures of merit (linear dynamic ranges for calibration curves and limits of detection) for the HPLC method (UV-vis and fluorescence detection) and for LETRSS. They demonstrate that LETRSS provides an improvement of at least two orders of magnitude in the limits of detection of the five dibenzopyrene isomers.
• The research will provide two procedures for interfacing LETRSS with HPLC analysis.
Dr. Orven Swenson reports that work continued with the fast GC interfaced with a laser ionization detector (LID). Initially, the gas flow from the fast GC was passed through the apex of a half-cylinder electrode so that the eluent intersected the laser at right angles. The emitted analyte is in a concentrated gas pulse compared to the ambient levels present in the detector half cylinder. The initial approach was to have the laser beam selectively ionize the aromatics in the concentrated pulse before it dispersed in the open half cylinder. With the open half cylinder, it was found that ambient conditions, such as relative humidity, air currents in the room, and temperature, affected the waveforms and made it impossible to determine if the shifts were because of differences in ion mobility or the other variables.
A new detector was designed and machined with a smaller half cylinder from a block of aluminum. To minimize the effects of ambient conditions on the detector, the new cell was enclosed and uniformly heated. The new detector cell performed significantly better than the previous half-cylinder detectors.
A Synoptics microlaser that operates at 8 kHz was integrated with the fast GC. At 8 kHz, the waveforms overlap so that there is no additional information produced by capturing the waveforms individually. A standard GC FID was successfully interfaced with the half-cylinder detector without additional amplification of the signal. A cocktail of five aromatics (benzene, toluene, ethylbenzene, orthoxylene, and isopropylbenzene) was successfully separated in a 30 second elution from the fast GC and detected with the LID.
Future Activities:
Future activities involve no major changes in research directions for the final year of the research project. Dr. Borgerding plans on using the ArSLID built in the preceding year with a fast GC for direct measurement of aromatics in water. Dr. Swenson plans to follow up on preliminary measurements that indicate ion mobility shifts in the peaks for different species in his integrated microlaser fast GC that may provide two-dimensional data when combined with the chromatograms.
Journal Articles on this Report : 4 Displayed | Download in RIS Format
Other project views: | All 6 publications | 6 publications in selected types | All 6 journal articles |
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Type | Citation | ||
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Arruda AF, Goicoechea HC, Santos M, Campiglia AD, Olivieri AC. Solid-liquid extraction room temperature phosphorimetry and pattern recognition for screening polycyclic aromatic hydrocarbons and polychlorinated biphenyls in water samples. Environmental Science and Technology , 2003; 37(7): 1385-1391. |
R829415E02 (2003) R829415E02 (Final) R828081E01 (Final) |
not available |
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Bystol AJ, Thorstenson T, Campiglia AD. Laser-induced multidimensional fluorescence spectroscopy in Shpol’skii matrixes for the analysis of polycyclic aromatic hydrocarbons in HPLC fractions and complex environmental extracts. Environmental Science and Technology 2002; 36(20):4424-4429. |
R829415E02 (2003) R828081E01 (Final) |
not available |
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Bystol AJ, Yu SJ, Campiglia AD. Analysis of polycyclic aromatic hydrocarbons in HPLC fractions by laser excited time resolved Shpol’skii spectrometry with cryogenic fiber optic probes. Talanta 2003;60(2-3):449-458. |
R829415E02 (2003) |
not available |
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Meyer MJ, Schieffer G, Moeker EK, Broderson J, Swenson O, Borgerding AJ. Selective detection of volatile aromatic compounds using a compact laser ionization detector with fast gas chromatography. Analytical Chemistry , 2004; 76(6): 1702-1707. |
R829415E02 (2003) R829415E02 (Final) |
not available |
Supplemental Keywords:
ecosystem protection, environmental exposure and risk, geographic area, ecological indicators, ecology, ecology and ecosystems, ecosystem protection, ecosystem assessment, ecosystem indicators, BTEX, North Dakota, ND, chemical characteristics, ecoindicator, ecological exposure, estuarine ecoindicator, hydrocarbon, water, drinking water, watersheds, groundwater, exposure, risk, chemicals, volatile organic compound, VOC, polycyclic aromatic hydrocarbons, PAHs, solvents, organics, environmental chemistry, monitoring, analytical, measurement methods,, RFA, Scientific Discipline, Geographic Area, Ecosystem Protection/Environmental Exposure & Risk, Ecology, Ecosystem/Assessment/Indicators, Ecosystem Protection, Environmental Chemistry, State, Ecology and Ecosystems, Environmental Engineering, Ecological Indicators, monitoring, ecoindicator, ecological exposure, hydrocarbon, VOCs, PAH, BTEX, estuarine ecoindicator, North Dakota (ND)Progress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.